Potential energy surface and MULTIMODE vibrational analysis of C2H3+

Carter, S., Sharma, A.R., Wu, J.Y., Braams, B.J., Schneider, R., Shepler, B. and Bowman, J.M. (2006) Potential energy surface and MULTIMODE vibrational analysis of C2H3+. Journal of Chemical Physics, 125 (22). 224306. ISSN 0021-9606 doi: 10.1063/1.2402169

Abstract/Summary

A full dimensional, ab initio-based semiglobal potential energy surface for C2H3+ is reported. The ab initio electronic energies for this molecule are calculated using the spin-restricted, coupled cluster method restricted to single and double excitations with triples corrections [RCCSD(T)]. The RCCSD(T) method is used with the correlation-consistent polarized valence triple-zeta basis augmented with diffuse functions (aug-cc-pVTZ). The ab initio potential energy surface is represented by a many-body (cluster) expansion, each term of which uses functions that are fully invariant under permutations of like nuclei. The fitted potential energy surface is validated by comparing normal mode frequencies at the global minimum and secondary minimum with previous and new direct ab initio frequencies. The potential surface is used in vibrational analysis using the "single-reference" and "reaction-path" versions of the code MULTIMODE. (c) 2006 American Institute of Physics.